Oil-soluble reaction products of (a) a high molecular weight olefin polymer, acrylonitrile, chlorine, an amine and maleic anhydride, with (g) an aliphatic amines; and lubricant compositions containing the same

ABSTRACT

Oil-soluble products, suitable as dispersant additives for lubricants, are obtained by reacting (a) a high molecular weight olefin polymer, having an average molecular weight of at least about 600, with acrylonitrile, a halogen, e.g., chlorine, in the presence of a catalyst, e.g., iodine, (b) reacting the product of (a) with a primary aliphatic amine, (c) reacting the resultant product of (b) with maleic anhydride, and (d) reacting the product resulting from (c) with an aliphatic amine or polyamine containing at least one primary amino group per anhydride function on the product (c).

This is a division of application Ser. No. 477,667, filed June 10, 1974now U.S. Pat. No. 3914,203.

BACKGROUND OF THE INVENTION

Lubricant deterioration in high speed engines causes the formation oflacquer, and sludge, and carbon deposits on the interior surfaces of theengines, which accelerates wear and reduces engine efficiency. To reducethe tendency for such deleterious products to deposit on the surfaces ofthe engines, it is known to incorporate in the lubricating oil certainadditives having dispersancy and/or detergency properties.

The continuing search for and the necessity of having available ashlessdispersant and/or detergent additives for motor oils is well known.Since the development of positive crankcase ventilation systems (PCV)there is a greater demand for improved additives of such types.

Various products have been developed for the purpose of impartingdispersant and/or detergent properties to lubricating oils: such as, byway of example, neutral and over-based metallo-organic compounds such asalkaline salts of sulfonic acids, and of hydrocarbon-P₂ S₅ reactionproducts. In-service drawbacks of such additives include the formationof undesirable metal-ash thermal decomposition products. Other additionagents were amine salts, amides, and amides of polybutenyl-substitutedpolycarboxylic acids. Still other proposed additives were combinationsof alkaline earth sulfonates and Mannich condensation products ofalkyl-substituted hydroxyaromatic compounds, amines having at least onereplaceable hydrogen on a nitrogen atom; and aldehydes; alkaline earthsalts of such Mannich condensation products have also been proposed.

SUMMARY OF THE INVENTION

In accordance with the present invention, the herein-described products,useful as lubricant additives, are obtained by the process comprising(a) reacting, at a temperature of from about 60° F. to about 160° F.,from about 0.3 moles to about 2.5 moles of a high molecular weightolefin polymer, having an average molecular weight of at least about600, with from about 0.5 to about 7.5 moles of acrylonitrile, and fromabout 0.4 to about 2.0 moles of a halogen, such as bromine and chlorine,in the presence of from about 7.8 × 10⁻ ³ moles to about 0.02 moles of acatalyst, preferably such as iodine, suitably in the presence of asolvent or diluent, such as, for example, benzene, chlorobenzene,chloroform and the like; (b) reacting at a temperature of about 200°F. - 350° F. for about 1-6 hours, the product from the reaction (a) withsufficient amount of a primary aliphatic amine, preferably butylamine,to replace halogen atoms in the product from the reaction (a); then (c)reacting the resultant product from the reaction (b) with from about 0.2moles to about 1.5 moles of maleic anhydride at a temperature of about200° F. - 350° F. for a period of about 2-4 hours; and (d) reacting theproduct from the reaction (c), at a temperature of about 200° F. - 350°F. for a period of about 2-4 hours, with from about 0.2 moles to about1.5 moles of an aliphatic amine or polyamine containing at least oneprimary amino group per anhydride function on the reaction productobtained in reaction (c), and recovering the resultant product bywell-known means.

The high molecular weight olefin polymer reactant is preferably apolymer of a lower mono-olefin, e.g., an olefin of about 2-6 atoms,having an average molecular weight of at least about 600, preferablyfrom about 1,000 to about 100,000 or more. The sources of the olefinpolymer reactant include polymers of 1-mono-olefins, such as ethylene,1-butene, isobutene, as well as medial olefins such as 2-butene and thelike. Particularly preferred are the polymers of propene, and butenes,or mixtures thereof, having average molecular weights in the range offrom about 600 to about 3,000.

The amine reactants suitable for use in the reactions (b) and (d) of theprocess described above, are preferably aliphatic amines or polyaminesof the general formula H₂ N(CH₂)_(y) NH₂, wherein "y" is an integer ofabout 3 to 10, said amine containing up to about 10 carbon atoms in thealkyl group, and poly-alkylene polyamines of the general formula##STR1## wherein "A" is a divalent alkylene radical of about 2 to about6 carbon atoms, and "x" is an integer of from 1 to about 10.Illustrative of suitable amines are, methylamine, dibutylamine,cyclohexylamine, ethylene diamine, trimethylene diamine, hexamethylenediamine, diethylene triamine, triethylene tetramine, tetraethylenepentamine, tripropylene tetramine, and also cyclic and higher homologsof such amines such as, for example, piperazine andamino-alkyl-substituted piperazines, e.g., 1-(2-aminopropyl)piperazine,1--4-bis(2-aminoethyl)piperazine, 2-methyl-1-(2-aminobutyl)piperazine,bis NN' aminopropyl piperazine, and the like.

The chemical composition of the reaction product of this inventioncannot be characterized with preciseness by chemical structural formula.While it is believed that the reaction produces predominantly certainpolymer "imides", it is believed that minor amounts of other endproducts may also be formed. In view of the complex nature of theresultant reaction products, the precise composition of such productcannot be defined by its chemical structure, but rather must be definedby the method of preparation.

The reaction products of the herein-described invention are useful andeffective additives for oleaginous lubricant compositions to impartdesirable properties thereto when used in amounts of from about 0.1% toabout 10%. Suitable lubricating oil bases include mineral oils, i.e.,petroleum oils, shale oils, etc., synthetic lubricating oils, such asthose obtained by the polymerization of hydrocarbons, and otherwell-known synthetic lubricating oils, and lubricating oils of vegetableand animal origin. Concentrates of suitable oil bases containing morethan 10%, i.e., from about 10% to about 75%, or more, of additive of thepresent invention, alone or in combination with other well-knownadditives, can be used for blending with lubricating oils in proportionsdesired for particular conditions or use, to give a finished productcontaining the effective amount of the additive of the presentinvention.

PREFERRED EMBODIMENT OF THE INVENTION

The following examples are illustrative of preferred embodiments of thepresent invention:

EXAMPLE 1 Part a.

1320 grams (equivalent to 0.5 moles olefin content) of a polybutene,having an average molecular weight of about 2,000 was dissolved in 950ccs. of chlorobenzene. To the solution was added 80 ccs. ofacrylonitrile (about 2 moles) and 5 grams of iodine as catalyst. Thesolution was covered from light, and chilled to 60°-70° F., andmaintained at this temperature. Chlorine gas was introduced at the rateof No. 4 Rotameter readings per hour for three hours (equivalent to anexcess of about one mole). After the chlorine addition, the reactionmixture was stirred for one hour and worked up. 2436 grams of dilutedproduct with an activity of 65% was recovered.

Part b.

To one-third of the product recovered in Part (a) was added dropwise 7.5grams (a slight excess of 0.1 mole) of butylamine. After stirring forone hour, the solution was refluxed for two hours.

Part c.

To the reaction in Part (b) was added 13 grams (about 0.14 moles) ofmaleic anhydride and refluxing of the reaction mixture continued for twohours. A slight amount of the excess maleic anhydride was sublimed out.

Part d.

To the reaction mixture obtained in Part (c) was added 10 grams(equivalent to about 0.5 mole) of tetraethylenepentamine, and themixture refluxed for two hours. Seven grams of calcium hydroxide wasadded to remove all the halides in solution, the product filtered hotand then stripped of the solvent. The recovered product contained 0.465%nitrogen and was 49% active.

EXAMPLE II

The product in this Example was prepared essentially as the product ofExample I, above, except that in Part (d) of the Example, N,N'-Bisaminopropyl piperazine was used in place of thetetraethylenepentamine used in Example I, above. The recovered productcontained 0.4% nitrogen.

The effectiveness of the reaction products of the present invention aslubricant additive is demonstrated by the data in Table I below. Thesedata were obtained by the so-called Spot Dispersancy Test (SDT), whichis a measure of the dispersancy property of the additive, and theso-called Hot Tube Test (HTT) for evaluating the thermal stability andoxidation resistance of the additive.

In the Spot Dispersancy Test, a measured amount of the additive to betested is mixed with a measured volume of crankcase lubricating oilformulation which has been used in a Lincoln Sequence V engine test for394 hours (twice the time of the standard test time). This compositionis heated and stirred at about 300° F. for about 16 hours and an aliquotis transferred to blotting paper. A control is made at the same time bystirring and heating at 300° F. for 16 hours a second oil from the 394hour Lincoln Sequence engine test, and depositing an aliquot on blottingpaper. At the same time, a readily available commercial ashlessdispersant is mixed in the same manner as above, for comparisonpurposes. The deposits on the blotting paper are measured to obtain theaverage diameter of the outer oil ring (Do), and the average diameter ofthe inner sludge ring (Da). The ratio of Da/Do is an indication of thedetergent-dispersant property of the addition agent.

The Hot Tube Test is used to evaluate the high temperature detergencyvalue of oils used in diesel applications. In this test the oil ispassed through a 16 inch, 8mm ID, glass tube, six inches of which isheated to a top temperature of 495° F. by means of heat transfer from analuminum block. The block is heated at one end and causes a temperaturegradient along the length of the glass tube, similar to the temperaturegradient along an engine piston. Oil is passed through the glass tube atthe rate of 0.1 cc per minute, along with air being introduced at therate of 20 ccs. per minute. At the end of the 100 minute test period,the glass tube is removed, cooled, and washed with hexane. Lacquer inthe five inches of the glass tube which was in the heated aluminum blockis rated by color on a scale of 1 to 10, the former value indicating aclean tube, and the latter value indicating a black tube. Lacquer formedin the glass tube below the heated block is rated by letter, A beingnone or very little, very light amber lacquer, B being up to one inch oflight amber lacquer, etc. The final rating of that portion of the tubein the heated block is a weighted average, of the various ratingspresent, based on the variation of lacquer along the length of the tube(as opposed to area coverage).

The following oil compositions were used in making the above tests andwere as follows:

    ______________________________________                                        Components           Sample A  Sample B                                       ______________________________________                                        Over-based Magnesium Sulfonate                                                                     2.0%      2.0%                                           Zinc Dialkyl* Dithiophosphate                                                                      1.1%      1.1%                                           Pour Point Depressor 0.5%      0.5%                                           Solvent-extracted SAE 5 Oil                                                                        21.7%     21.7%                                          Solvent-extracted SAE 10 Oil                                                                       70.2%     70.2%                                          Product of Example I 4.5%      --                                             Product of Example II                                                                              --        4.5%                                           ______________________________________                                         *From mixture of isopropyl and decyl alcohols                            

                  TABLE I                                                         ______________________________________                                                      TYPE OF TEST                                                    SAMPLE          SDT*        HTT**                                             ______________________________________                                        A               87.5        8.8A                                              B               84          7.3B                                              ______________________________________                                         Rating:                                                                       *90, Excellent; 85, very good; 80, Pass                                       **10A, Perfect                                                           

The data in the above Table I demonstrate the effectiveness of theproducts of the present invention as detergent-dispersant additives inlubricating oils for use in automobile and diesel engines.

Percentages given herein and in the appended claims are weightpercentages unless otherwise stated.

Although the present invention has been described with reference tocertain specific preferred embodiments thereof, the invention is notlimited thereto, but includes within its scope such modifications andvariations as come within the scope and spirit of the appended claims.

I claim:
 1. A lubricant composition comprising a major amount of anormally liquid oleaginous lubricant, and from about 0.1% to about 10%of the oil-soluble product obtained by the process comprising reacting(a) from about 0.3 moles to about 2.5 moles of a high molecular weightolefin polymer having an average molecular weight of at least 600, withfrom about 0.5 moles to about 7.5 moles of acrylonitrile, and from about0.4 to about 2.0 moles of chlorine or bromine iodine catalyzed at atemperature of from about 60° F to about 160° F; (b) reacting, at atemperature of from about 200° F to about 350° F for a period of about 1to 6 hours, the product of (a) with sufficient amount of primaryaliphatic hydrocarbyl amine to replace the halogen atoms in the productof reaction (a); (c) reacting the product of (b) with from about 0.2moles to about 1.5 moles of maleic anhydride at a temperature of fromabout 200° F to about 350° F for a period of about 2--4 hours; and (d)reacting at a temperature of from about 200° F to about 350° F, theproduct of reaction (c) with from about 0.2 moles to about 1.5 moles ofprimary aliphatic hydrocarbyl amine containing at least one primaryamino group per anhydride function in the reaction product of (c). 2.The lubricant composition of claim 1 wherein the olefin polymer reactantis a polybutene.
 3. The lubricant composition of claim 1 wherein theolefin polymer reactant is a polypropene.
 4. The lubricant compositionof claim 2 wherein the amine reactant of (b) is butylamine.
 5. Thelubricant composition of claim 4 wherein the aliphatic hydrocarbyl amineof (d) has the formula H₂ N(CH₂)yNH₂ or H₂ N(A-NH)_(x) H in whichformulae y is an integer from 3 to 10, A is a divalent hydrocarbonradical containing from 2 to 10 carbon atoms and x is an integer from 1to
 10. 6. The lubricant composition of claim 4 wherein the primaryaliphatic hydrocarbyl amine of d is tetraethylenepentamine.
 7. Thelubricant composition of claim 4 wherein the primary hydrocarbyl amineof (d) is N,N-bisaminopropyl piperazine.